Substituted diacetylbenzenes reacted with an amine to yield a colored product for dyeing hair



United States Patent France No Drawing. Filed May 29, 1961, Ser. No. 133,13 Claims priority, application France, June 2, 1960, 828,9fi6, Patent 1,304,654

7 Claims. (Cl. 1167-83) This invention relates to the dyeing of hair.

It is known that hair dyeing can be carried out with so-called oxidation dyes. The coloration obtained in this case is the result of an oxidation which, after penetration of the colorless starting material into the hair, converts it to a colored compound. The oxidation can be carired out with the aid of atmospheric oxygen or of various oxidizing agents, if desired in the presence of catalysts.

This process has various disadvantages. So-called oxidation dyes are generally physiologically active and often give rise to allergic reactions. Moreover, they are usually unstable products which oxidize readily, which does not facilitate their storage or their handling. They are used in the form of very complex mixtures and the shades obtained are often difficult to reproduce. The solutions in which these dyes are applied are often at very high pH values and, in addition, the production of the dyeing effect necessitates an additional oxidizing operation.

After known dyeing process consists in operating with so-called direct dyes, which are already colored at the outset and act by diffusion in the fibre. In this case, the dyes are not required to undergo any subsequent chemical transformation. The dyes employed in these processes give weak and superficial dyeing effects and the dyeing process generally necessitates application of heat. Moreover, the dyeing effect obtained lasts only a short time.

It is an object of the present invention to provide a new hair dyeing process by means of which the aforesaid disadvantages can be obviated.

According to the present invention there is provided a process for dyeing hair which comprises impregnating the hair with a solution containing one or more diketone compounds of the formula:

in which R and R represent lower aliphatic radicals containing from 1 to 4 carbon atoms and X represents a substituted or unsubstituted aromatic residue or a cycloaliphatic residue comprising one or more double bonds, the carbonyl chains being attached to these cyclic residues in the ortho-position in relation to one another, allowing the said solution to remain in contact with the hair and causing or permitting reaction of the said diketone compound or compounds with one or more compounds comprising one or more free amino groups naturally present on the hair or previously or simultaneously deposited or formed thereon.

Particularly suitable substances conforming to the above-defined general formula are:

1 2-diacetylbenzene COCH;

COCHa 3,158,542 Patented Nov. 24, 1964 4-nitro-1 2-diacetylbenzene NOg- O OCH;

\ C 0 CH 5 G-dimethoxy-2-acetylpropiophenone COCH3 C H 0 C O C H}; 0 H;

1 2 2-(liacety1-cyclohex-4-ene COCH3 COCH The preparation of the diketones of the present application are shown in the following references:

(a) For the preparation of the ortho-diacetylbenzene:

F. Weygaud, Weber, Ber. 89, 1994-99 (1956).

(b) For the preparation of the dimethoxy-5,6-acetyl-2- propiophenone: F. Weygaud, Weber, Ber. 90, 1889 1957 (c) For the preparation of nitro-4, diacetyl-l,2-benzene:

R. Riemschneider, Ber. 92, 1709 (1959).

(d) For the preparation of 1,2-diacetyl-cycl0heXene-4:

Sopov, Zhur, Obshchel, Khim. 26, 16029 (1956).

The process according to the invention, in which the development of the desired shade takes place in situ, has the advantage that it gives a dyeing effect of remarkablefastness which resists rubbing and light. In addition, very varied colors can be produced therewith, depending upon the various inter-reacting compounds. So far as is known the diketones are completely without deleterious physiological effect.

The diketone compound employed is chosen in accordance with the dyeing shade which it is desired to obtain. The concentration of the diketone compound in the aqueous solution employed may be varied but is preferably between 0.1% and 10%.

In one method of carrying out the process of the invention the hair is first brought into contact with an aqueous solution of the diketone compound and this solution is allowed to act for a time sufficient to permit the penetration of the hair and to permit reaction of the ketone compound with compounds having a free amino group which are naturally present on the hair. No previous treatment of the hair is necessary. This procedure is particularly advantageous when it is applied to bleached hair, since the partial hydrolysis of the peptide bond, consequent upon the action of the bleaching agents, has the effect of freeing a proportion of the amino groups of the amino-acids or oligo-peptides constituting the hair, and these amino groups react with the aforesaid ketone compounds.

In a further process according to the invention the hair is pro-impregnated With the solution of an amino compound, the excess of solution of amino compound is re moved and the aqueous solution of ketonic product is applied.

In a further alternative procedure the aqueous solution of the amino compound is mixed, at the time of use, with the aqueous solution of the ketone derivative and the resulting mixture applied to the hair.

Amino compounds suitable for impregnation of the hair are, for example, natural amino acids, aliphatic, cyclic or aromatic monoor polyamides, and their salts. The concentration of the amino compounds may vary between wide limits. They are preferably employed in 3 concentration between 0.01% and 20% in aqueous solution.

The following examples will serve to illustrate the invention:

Example I A lock of 100% white hair is impregnated at room temperature with a 1% aqueous solution of orthodiacetylbenzene. After 10 minutes, the hair is washed, rinsed and dried. A mauve-pink shade is obtained.

Example II A lock of 100% white hair is impregnated with a 5% aqueous solution of monoethanolamine, dried between two sheets of filter paper and then immediately impregnated with a 1% aqueous solution of ortho-diacetylbenzene with the aid of a small brush. Contact is maintained for S to minutes. The lock is then rinsed, shampooed, rinsed again and dried under a hood. The tint obtained is a strong reddish-violet.

Example 111 A lock of 100% white hair is immersed in a 5% aqueous solution of ammonium carbonate. Excess liquid is removed by placing the lock between two sheets of filter paper and the lock is then impregnated with a 1% aqueous solution of orthodiacetylbenzene. Contact is maintained for 5 to 10 minutes. The lock is then rinsed, shampooed and rinsed again. After drying under a hood, the shade obtained is a violet-pink.

Example IV 100% white hair is impregnated with a 6% aqueous solution of ethylenediamine carbonate, excess liquid removed, and then impregnated with a 1% aqueous solution or orthodiacetylbenzene. Contact is maintained for 5 to 10 minutes. The hair is then rinsed, shampooed and rinsed again. After drying, an attractive russet blonde shade is obtained.

Example V 100% white hair is impregnated with the following mixture:

1% aqueous solution of monoethanolamine cc 5 1% aqueous solution of diacetylbenzene cc 5 by means of a small brush.

Contact is maintained for 5 to 10 minutes. The hair is then rinsed, shampooed, rinsed again and dried under a hood. A grey-blue shade is obtained.

Example VI A look of 100% white hair is impregnated with a mixture of 5 cc. of a 5% aqueous solution of piperazine and 5 cc. of a 1% aqueous solution of orthodiacetylbenzene. Contact is maintained for 10 minutes and the hair is then washed and dried. An ash-blonde shade is obtained.

Example VII A lock of 100% white hair is impregnated with a mixture of 5 cc. of a 6% aqueous solution of ethylenediamine carbonate and 5 cc. of a 1% aqueous solution of orthodiacetylbenzene. Contact is maintained for 10 minutes and the hair is then washed and dried. A light russet-blonde shade is obtained.

Example VIII 100% white hair is impregnated with a 5% solution of piperazine carbonate in aqueous alcohol (:20). After a period of action of 10 minutes, the hair is dried with a towel and there is applied a solution of:

1 Z-diacetylbenzene g 3 Product of condensation of ethylene oxide with branched dodecylmercaptan, known under the name NONIC 218 g 10 After a period of action of 15 minutes, the hair is washed and dried. A light mahogany shade is obtained.

Example IX white hair is impregnated with a solution having the following composition:

Allylamine carbonate g 5 5:6-dimethoxy-2-acetylpropiophenone g 1 Water to make 100 cc.

After a period of action of 10 minutes, the hair is dried with a towel and a dilute acetic acid solution is applied. Contact is maintained for 10 minutes. The hair is then washed and dried. A grey-green shade is obtained.

What I claim is:

1. A process for dyeing live human hair which comprises; impregnating the hair with a solution containing about 0.1% to 10% of at least one of the diketone compounds selected from the group consisting of 1,2- diacetylbenzene, 4 nitro 1,2 diacetylbenzene, 5,6-dimethoxy-Z-acetyl propiophenone and 1,2-diacetyl-cycloheX-4-ene, allowing the solution to remain in contact with the hair for a period of time preferably between 5 minutes and 10 minutes so as to permit the said solution to penetrate the hair and react with a compound comprising free amino groups present on the hair.

2. A process according to claim 1, wherein the compounds containing the free amino groups are naturally present on the hair.

3. A process according to claim 1, wherein the compounds containing the free amino groups are previously deposited on the hair.

4. A process according to claim 1, wherein the compounds containing the free amino groups are simultaneously deposited on the hair.

5. A process according to claim 1, wherein the compounds containing the free amino groups are formed on the hair.

6. A process according to claim 1, wherein the hair is impregnated with the solution of an amino compound, the excess solution of the amino compound is removed and the hair is then impregnated with a solution of at least one of the said diketone compounds.

7. A process according to claim 1, wherein the diketone and the amino compound are mixed in aqeous solution and the resulting mixture applied to the hair.

References Cited in the file of this patent Chemical Abstracts 53:15,174b (Abstract of Acta Histochem, 6, 276-94 (1959)).

Chemical Abstracts 1V 54:19,820h (Abstract of Acta' Histochem, 9, 11-65 (1960) Chemical Abstracts V 51:5882h (Abstract of Acta Histochem, 3, -63 (1956)).

Chem. Abst., vol. 50, 1956, page 731.

Chem. Abst., vol. 37, 1943, page 5752. 

1. A PROCESS FOR DYEING LIVE HUMAN HAIR WHICH COMPRISES; IMPREGNATING THE HAIR WITH A SOLUTION CONTAINING ABOUT 0.1% TO 10% OF AT LEAST ONE OF THE DIKETONE COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF 1, 2DIACETYLBENZENE, 4 - NITRO - 1,2 - DIACETYLBENZENE, 5, 6-DIMETHOXY-2-ACETYL PROPIOPHENONE AND 1,2-DIACETYL-CYCLOHEX-4-ENE, ALLOWING THE SOLUTION TO REMAIN IN CONTACT WITH THE HAIR FOR A PERIOD OF TIME PREFERABLY BETWEEN 5 MINUTES AND 10 MINUTES SO AS TO PERMIT THE SAID SOLTUTION TO PENTRATE THE HAIR AND REACT WITH A COMPOUND COMPRISING FREE AMINO GROUPS PRESENT ON THE HAIR. 